Color forming compounds containing sulphonamide groups



Patented Dec. 12, 1944 COLOR FORMING COMPOUNDS CONTAINING SULPHONAMIDEGROUPS Paul W. Vittum, Willard D. Peterson, and Henry D. Porter,Rochester, N. Y.. assignors to Eastman Kodak Company, Rochester, N. Y.,a corporation of New-Jersey No Drawing. Application July 26, 1941,Serial No.

404,235. In Great Britain March 31, 1939 7 Claims.

This invention relates to photographic color forming compounds andparticularly to color forming coupler compounds containing sulphonamidegroups.

This application is a continuation-in-part of our application Serial No.266,152, filed April 5, 1939, now Patent 2,271,238, granted January 27,

The use of color forming compounds which react with the developmentproduct of primary aromatic amino developing agents toform. color imageson photographic development is well known and has been the subject ofnumerous prior patents. The dyes formed in this way are insoluble inwater and in the ordinary photographic developing and fixing bathsalthough the silver images formed simultaneously with them during thephotographic development may be removed from the photographic layer toleave pure dye images in the layer. The coupler compounds used in thisway may be added to the developing solution orin certain cases may beincorporated in the photographic layer prior to exposure. When thecoupler compounds are incorporated in the developing solution, it isdesirable that they be sufliciently soluble in the developing solutionso that amounts may be used which produce suf ficiently high dyedensities in the resulting photographic image. In many cases the couplercompounds are not sufliciently soluble in the developer and steps mustbe taken to increase their solubility.

In Schinzel application Serial No. 263,945, filed March 24, 1939, acontinuation-in-part of Serial No. 151,811, filed July 3, 1937, nowPatent 2,306,- 410, granted December 29, 1942, phenolic and naphtholiccoupler compounds are described which contain sulphonamide groups inwhich the sulphur of the sulphonamide is attached to the phenol ornaphthol. These compounds are highly soluble in the developing solutionsand produce dyes which are transparent and are not cloudy or opaque asis the case with many dyes produced in this way. These dyes are,however, subject to decomposition by the' action of heat and light andit is, therefore, desirable to produce dyes having the solubility andlight transmission characteristics of the dyes described in the Schinzelapplication but which are more stable to heat and light. I

' It is, therefore,'an object of the present invention to provide novelphotographic {coupler compounds having desirable properties with respectto heat and light stability. A further object is to provide photographiccouplers which are highly soluble in developing solutions. A stillfurther object is to provide photographic couplers which producetransparent dyes on photographic development. A still further object isto provide coupler compounds which produce dyes --of desirable lighttransmission characteristics for multicolor photography. Other objectswill appear from the following description of our invention.

These objects are accomplished by the use of certain coupler compoundscontaining sulphon' amide groups.

The color-forming compounds which we have found to be useful arecompounds of the general structure A R-SOzNH-R' R-NHSOr-B' in which Rrepresents a substituted or unsubstituted aryl radical or alky1 radicaland R represents a cyanoacetylaryl group, such as a cyanoacetylphenyl orcyanoacetylnaphthyl group, or a cyanoacetanilide group.

Compounds suitable for use according to our invention are as follows:

O-s OTNHOCOCHZCN p-(beuzenesulphonamino)-benzoyl acetonitrile4-(benzenesulphonamino)-2-naphthoyl-acetonitrilc O-s mNHQ-NH-COCmCNp-benzenesulphonamino-cyanoacetanilide Mafia2-cyanoacetyl-7-(p-laurylbenzenesulphonamino)-naphthalene NH-430 mm:

8 O ;-NH C 0 p-(cyanoaoetamino)-benzenesulphonanilide (EOCHZCN QOCHiQNNH-S Oz- S O n-NH N,N-di-(p-cyanoacetylphenyl)-benzene-l,3-disulphonamide C 0 CHzUN m-(methanesulphonamino)-benzoylacetonitrile IrTH-C 0-CH2CN NH-SOz-OB:

p-(4-bromobenzenesulphonamino)-cyanoacetanilide The coupler compoundshaving the general formula: Y

' R--S0iNH-R' R---NHSO2R contain a methylene group which is reactivewith the oxidation product of primary aromatic amino photographicdevelopers to produce magenta dyes. The following example, which isillustrative only, is a developing solution containing a couplersuitable for use according to our invention.

In the foregoing example, we have described adding the coupler compoundto the developing solution itself. Although it will usually be employedin this way, the coupler compound may In the case'of a multi-layerphotographic him in which color forming compounds ma be incorporated inone or more of the layers, it may be necessary to take specialprecautions to prevent wandering of the coupler compound from thesensitive layer in which it is incorporated.

Certain of the coupler compounds described in the present applicationare in themselves nondifiusing and may be incorporated in thephotographic layer without the use of additional agents to preventdiffusion. The compound 2- cyano-acetyl-7 (p-laurylbenzenesulphonamino)naphthalene is an example of this type coupler.

The sulphonamide group, because of its solubilizing efiect, has a veryimportant advantage in connection with non-diffusing couplers in that itmakes dispersion of the couplers very much easier. Thus it is possibleto have a coupler of high molecular weight which is completelynondifiusing and yet which is simply and easily dispersed due to thesalt-forming properties of the SO2'-NH group. p

The aromatic amino developing agents used with the coupler compounds ofour invention include the mono, di and tri-amlnoaryl compounds and theirderivatives formed. by substitution in the amino group as well as in thering, such as alkylphenylenediamines and alkyltoluylenediamines. Thesecompounds are usually used in the salt form, such as the hydrochlorideor the sulphate, which are more stable than the amines themselves.Suitable compounds are diethyl-p-phenylenediamine hydrochloride,monomethyl p phenylenediaminehydrochloride,dimethyl-p-phenylenediaminehydrochloride anddimethyl-p-phenylenediaminesulphate. The paminophenols and theirsubstitution products may also be used where the amino group isunsubstituted. All of these compounds have an unsubstituted amino groupwhich enables the oxidation products of the developer to couple with thecolor forming compounds to form a dye image.

Our development process may be employed for the production of coloredphotographic images in layers of gelatin or other carrier, such ascolalso be incorporated in the photographic layer prior to exposure andthe colored image formed by development of the layer in the primaryaromatic amino developing solution. Special distain cases the couplermay be absorbed or adsorbed to the sensitive salt or may be combinedwith the sensitive salt as a chemical combination.

lodion, organic esters of cellulose, or syntheticof the support. Thesuperposed layers may be difierentially sensitized and the dyes formedtherein by coupling may be bleached by an oxidizing agent such aschromic acid to colorless.

soluble compounds. The destruction of the dye in this way does-notdestroy the silver image and a silver image may be developed, bleachedand developed to color a number of times, thus permitting the formation.of natural color images in superposed layers as described, for ex-'ample, in Mannes and Godowsky U. S. Patent No. 2,l13,329.

The examples and compounds set forth in the ,present specification areillustrative only and it is to be understood that our invention is to betaken as limitedonly by the scope of the appended claims. Where wedescribe organic groups such as aryl, arylene, alkyl, and sulphonamidein the specification and claims, we intend to include the substituted,as well as unsubstituted, groups, except' where certain groups arespecifically excluded.

We claim:

1. A color-forming photographic developer comprising a primary aromaticamino developing agent and a coupler compound having a formula selectedfrom the group consisting of R-SOzNH--R' where R is selected from thegroup consisting of alkyl and aryi radicals and R is a cyanoacetylarylgroup.

2. A color-forming photographic developer comprising a primary aromaticamino developing agent and a coupler compound having the. formula '4R-SO2NHR'-COCH2CN are,

developing agent in the presence of a coupler compound having a formulaselected from the group consisting of Rv-SOQNH-R' and R-NHSOr-R' where Ris selected from the group consisting 01' alkyl and aryl radicals and Ris a cyanoacetylaryl group.

6. A photographic emulsion for forming colored images comprising acolloidal carrier con-' taining a sensitive silver halide\ and a=couplercompound having a formula selected from the group consisting ofR-SOaNH-R and R-NHSOz-R' where R, is selected from the group consistingof alkyl and aryl radicals and R is a cyanoacetylaryl grouD.-

'7. A photographic emulsion for forming colored images comprising acolloidal carrier containing a sensitive silver halide and2-cyanoacetyi-l- (p-laurylbenzenesulphonamino) naphthalene as a coupler.

PAUL w. wmmnn D. ra'ransou.

HENRY n. PORTER.

